CN102731891B - Thermoplastic oil-resistant halogen-free low-smoke flame-retardant polyolefin cable material and preparation method thereof - Google Patents
Thermoplastic oil-resistant halogen-free low-smoke flame-retardant polyolefin cable material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 239000000779 smoke Substances 0.000 title claims abstract description 31
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 30
- 239000003063 flame retardant Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 10
- 229920001169 thermoplastic Polymers 0.000 title abstract description 10
- 239000004416 thermosoftening plastic Substances 0.000 title abstract description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 17
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 238000005469 granulation Methods 0.000 claims abstract description 4
- -1 butylene, propylene Chemical group 0.000 claims description 17
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 7
- 235000019260 propionic acid Nutrition 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 20
- 239000002480 mineral oil Substances 0.000 abstract description 12
- 235000010446 mineral oil Nutrition 0.000 abstract description 12
- 230000008859 change Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 abstract 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 5
- 239000004707 linear low-density polyethylene Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a thermoplastic oil-resistant halogen-free low-smoke flame-retardant polyolefin cable material. The material is characterized in that: the material is prepared from raw materials of: substrate resin, a fire retardant, a lubricating agent, and an anti-oxidant. The substrate resin is composed of metallocene linear low-density polyethylene (MLLDPE), an ethylene-vinyl acetate polymer, and an interface compatibilizing agent. The preparation method comprises the steps that: the raw materials are well mixed in a high-speed mixing machine; the mixture is subjected to mixed extrusion under a processing temperature of 125-145 DEG C on a same-direction double-screw extruder; and the material is subjected to hot-cut granulation, such that a finished product is obtained. Compared with a traditional thermoplastic halogen-free low-smoke flame-retardant polyolefin cable material, the cable material provided by the invention has good oil resistance. When the cable material is soaked in mineral oil, the change rates in tensile strength and breaking elongation are low.
Description
Technical field
The present invention relates to a kind of thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material and preparation method thereof, belong to wire cable insulating and the technical field of material (abbreviation CABLE MATERIALS) for sheath.
Background technology
Traditional halogen-free low-smoke flame-resistant polyolefin cable material is main resin base material mainly with ethylene-vinyl acetate copolymer (EVA), is aided with the high temperature resistant deformability that a small amount of linear low density polyethylene (LLDPE) improves CABLE MATERIALS.Therein ethylene-vinyl acetate copolymer is to be made by ethene (E) and vinyl acetate (VA) copolymerization, is called for short EVA, has good flexibility and elasticity.It is solid at normal temperatures, and heating melting becomes the liquid that can flow and have certain viscosity to a certain extent.And linear low density polyethylene is that some multipolymers with short-chain branch generate by copolymerization on poly main chain.
If it is exactly thermoplastic that traditional halogen-free low-smoke flame-resistant polyolefin cable material does not need to accept cross-linking radiation, it is thermoplasticity halogen-free low-smoke flame-resistant polyolefin cable material, but this thermoplastic halogen-free and low-smoke flame-retardant polyolefin CABLE MATERIALS is difficult to by soaking mineral oil experimental test in GB/T2951.21-2008, it is its resistance to mineral oil poor performance, therefore this product just can not be applied to tank wagon, transition pipeline etc. has in the environment of mineral oil, and its application scenario is restricted.The poor reason of tradition thermoplastic halogen-free and low-smoke flame-retardant polyolefin CABLE MATERIALS oil resistant is: the EVA in raw material is subject to the impact of Vinyl Acetate Monomer, and degree of crystallinity is lower, causes EVA swelling rate in mineral oil larger, and oil resistant is poor.In addition, for guaranteeing the characteristic of Halogen and low-smoke and flame retardant, in this CABLE MATERIALS, will add inorganic combustion inhibitor, and inorganic combustion inhibitor also can destroy crystalline region, jointly make to take the resistance to mineral oil poor performance of the thermoplastic halogen-free and low-smoke flame-retardant polyolefin CABLE MATERIALS that EVA is main base material.LLDPE, therefore it has higher degree of crystallinity, and resistance to mineral oil performance is under the same conditions better than EVA, but inorganic combustion inhibitor is sneaked into after LLDPE, can affect anti-cracking performance, make its elongation at break and heat-resisting cracking performance cannot meet national standard requirement.
Summary of the invention
The object of the invention is to provide a kind of thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is: a kind of thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material, and composition of raw materials is mainly comprised of the material of following mass parts:
(1) matrix resin is 100 parts;
Described matrix resin is comprised of the material of following mass parts:
1. metallocene linear-low density polyethylene is 35～85 parts;
2. ethylene-vinyl acetate copolymer is 10～40 parts;
3. interfacial compatibilizer is 5～30 parts;
Wherein, described metallocene linear-low density polyethylene is that the 3rd monomer is hexene, octene, butylene, propylene or any two kinds of metallocene catalysed polyethylene with ethene terpolymer wherein, and its melt flow rate (MFR) is less than or equal to 5 grams/10 minutes;
The vinyl acetate content of described ethylene-vinyl acetate copolymer is less than 30%, and melt flow rate (MFR) is less than or equal to 10 grams/10 minutes;
Described interfacial compatibilizer is the maleic anhydride grafts of the multipolymer of a kind of monomer in ethene and vinyl acetate, methyl acrylate, propylene, butylene, hexene and octene, and melt flow rate (MFR) is less than or equal to 3 grams/10 minutes;
(2) fire retardant is 130～170 parts;
The fire retardant material of described fire retardant is aluminium hydroxide or magnesium hydroxide, and this fire retardant material carries out surface modification through silane coupling agent, and the meta particle diameter of wherein said aluminium hydroxide is less than 2 microns;
(3) lubricant is 1～5 part;
Described lubricant is selected from a kind of in Zinic stearas, Magnesium Stearate, polyethylene wax;
(4) oxidation inhibitor is 0.5～3 part;
Described oxidation inhibitor is selected from four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, Tyox B, propionic acid stearyl alcohol ester, 2,6 ditertbutylparacresols, 1,1, a kind of in 3 three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, three ［ 2,4-di-tert-butyl-phenyl ］ phosphorous acid ester.
Preferably, a kind of thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material, composition of raw materials is mainly comprised of the material of following mass parts:
(1) matrix resin is 100 parts;
Described matrix resin is comprised of the material of following mass parts:
1. metallocene linear-low density polyethylene is 50～70 parts;
2. ethylene-vinyl acetate copolymer is 20～30 parts;
3. interfacial compatibilizer is 10～20 parts;
(2) fire retardant
Use silane coupling agent to carry out 140～160 parts, the aluminium hydroxide of surface modification;
(3) lubricant is 2～4 parts;
(4) oxidation inhibitor is 1～2 part.
Preferably, described oxidation inhibitor is four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester.
Preferably, the maleic anhydride grafts that described interfacial compatibilizer is ethene-hexene copolymer, or be the maleic anhydride grafts of ethylene-octene copolymer.
For achieving the above object, the first scheme that the present invention adopts is: a kind of method of preparing thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material, by described matrix resin, fire retardant, lubricant and oxidation inhibitor after high-speed mixer fully mixes, on parallel dual-screw extruding machine, at 125～145 ℃, processing temperature interval, mix and extrude, earnestly granulation.
Related content in technique scheme is explained as follows:
1,, in such scheme, described four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester is called for short antioxidant 1010.
2,, in such scheme, described metallocene linear-low density polyethylene (MLLDPE) refers to the linear low density polyethylene (LLDPE) of being produced as catalyzer by metallocene." luxuriant " in metallocene claims again ring luxuriant diene, can form complex compound with metal, is " metallocene ", can be used as the poly catalyzer of preparation, and feature is that high, the applicable monomer of catalytic activity is many, polymer architecture can accurately be controlled etc.Be different from the LLDPE that traditional Ziegler-Natta catalyst is produced, metallocene is as a kind of single-point catalyst, the MLLDPE producing has narrow relative molecular weight and distributes, the alpha-olefin comonomer that polymerization adds is evenly distributed, can obtain the height stereoregular product of alpha-olefin, therefore, MLLDPE has the degree of crystallinity higher than LLDPE, intensity and toughness.Select suitable MLLDPE as the main component of thermoplastic halogen-free and low-smoke flame-retardant polyolefin CABLE MATERIALS matrix resin, to have utilized its higher degree of crystallinity, with the swelling rate of mineral oil to matrix resin that slow down, make product can pass through the experimental test of resistance to mineral oil in national standard, and CABLE MATERIALS also have good tensile strength and elongation at break.
3, in such scheme, described ethylene-vinyl acetate copolymer (EVA) is as the ancillary component of thermoplastic halogen-free and low-smoke flame-retardant polyolefin CABLE MATERIALS matrix resin, can effectively alleviate and take CABLE MATERIALS that MLLDPE the is main component melt fracture phenomenon in stranding process, improve the bright and clean degree on cable surface, improve elongation at break and the tensile strength of CABLE MATERIALS.
4, in such scheme, described meta particle diameter (D50) refers to corresponding particle diameter when cumulative particle sizes percentile reaches 50%, and D50 is commonly used to represent the mean particle size of powder.
5,, in such scheme, described " mass parts " refers to and take any quality as 1 part of content unit representing.
6,, in such scheme, the aluminium hydroxide of described fire retardant material is chemical synthesis aluminium hydroxide.
Because technique scheme is used, the present invention compared with prior art has following advantages and effect:
The present invention is the degree of crystallinity of having utilized MLLDPE higher, by blending and modifying, provide a kind of thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material, compare with common thermoplastic halogen-free and low-smoke flame-retardant polyolefin CABLE MATERIALS, the swelling rate of mineral oil to matrix resin can slow down, resistance to mineral oil performance is good, can be by the experimental test of resistance to mineral oil in national standard; In addition, cable any surface finish, tensile strength, elongation at break and heat-resisting cracking performance are all better.After the present invention mixes all raw materials during preparation, directly in parallel dual-screw extruding machine previous step, extrude and form, technique is simple, and facility investment is few.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment mono-: a kind of thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material and preparation method thereof
One, composition of raw materials
Two, preparation technology
The component of above-mentioned mass parts, after high-speed mixer fully mixes, on parallel dual-screw extruding machine, is mixed and extruded fervent granulation at 125～145 ℃, processing temperature interval.
Three, material behavior
The tensile strength of the thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material of preparing by above-mentioned composition and engineering is 13.6MPa, elongation at break 210%, limiting oxygen index(LOI) 34%, density 1.46g/cm
3, volume specific resistance 1.2 * 10
13Ω .m, sample is after 90 ℃ * 4h of IRM902 oil soaks, and the velocity of variation of tensile strength and elongation at break is all less than or equal to ± 20%.
Embodiment bis-: a kind of thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material and preparation method thereof
One, composition of raw materials
Two, preparation technology
With embodiment mono-.
Three, material behavior
The tensile strength of the thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material of preparing by above-mentioned composition and engineering is 12.2MPa, elongation at break 180%, limiting oxygen index(LOI) 36%, density 1.49g/cm
3, volume specific resistance 8.9 * 10
12Ω .m, sample is after 90 ℃ * 4h of IRM902 oil soaks, and the velocity of variation of tensile strength and elongation at break is all less than or equal to ± 20%.
Embodiment tri-: a kind of thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material and preparation method thereof
One, composition of raw materials
Two, preparation technology
With embodiment mono-.
Three, material behavior
The tensile strength 13.3MPa of the thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material of preparing by above-mentioned composition and engineering, elongation at break 220%, limiting oxygen index(LOI) 33%, density 1.45g/cm
3, volume specific resistance 7.5 * 10
12Ω .m, sample is after 90 ℃ * 4h of IRM902 oil soaks, and the velocity of variation of tensile strength and elongation at break is all less than or equal to ± 20%.
Above-described embodiment is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (5)
1. a thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material, is characterized in that: composition of raw materials is mainly comprised of the material of following mass parts:
(1) matrix resin is 100 parts;
Described matrix resin is comprised of the material of following mass parts:
1. metallocene linear-low density polyethylene is 35～85 parts;
2. ethylene-vinyl acetate copolymer is 10～40 parts;
3. interfacial compatibilizer is 5～30 parts;
Wherein, described metallocene linear-low density polyethylene is that the 3rd monomer is hexene, octene, butylene, propylene or any two kinds of metallocene catalysed polyethylene with ethene terpolymer wherein, and its melt flow rate (MFR) is less than or equal to 5 grams/10 minutes;
The vinyl acetate content of described ethylene-vinyl acetate copolymer is less than 30%, and melt flow rate (MFR) is less than or equal to 10 grams/10 minutes;
Described interfacial compatibilizer is the maleic anhydride grafts of the multipolymer of a kind of monomer in ethene and vinyl acetate, methyl acrylate, propylene, butylene, hexene and octene, and melt flow rate (MFR) is less than or equal to 3 grams/10 minutes;
(2) fire retardant is 130～170 parts;
The fire retardant material of described fire retardant is aluminium hydroxide or magnesium hydroxide, and this fire retardant material carries out surface modification through silane coupling agent, and the meta particle diameter of wherein said aluminium hydroxide is less than 2 microns;
(3) lubricant is 1～5 part;
Described lubricant is selected from a kind of in Zinic stearas, Magnesium Stearate, polyethylene wax;
(4) oxidation inhibitor is 0.5～3 part;
Described oxidation inhibitor is selected from four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, Tyox B, propionic acid stearyl alcohol ester, 2,6-ditertbutylparacresol, 1,1, a kind of in 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, three ［ 2,4-di-tert-butyl-phenyl ］ phosphorous acid ester.
2. thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material according to claim 1, is characterized in that: composition of raw materials is mainly comprised of the material of following mass parts:
(1) matrix resin is 100 parts;
Described matrix resin is comprised of the material of following mass parts:
1. metallocene linear-low density polyethylene is 50～70 parts;
2. ethylene-vinyl acetate copolymer is 20～30 parts;
3. interfacial compatibilizer is 10～20 parts;
(2) fire retardant
Use silane coupling agent to carry out 140～160 parts, the aluminium hydroxide of surface modification;
(3) lubricant is 2～4 parts;
(4) oxidation inhibitor is 1～2 part.
3. thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material according to claim 1, is characterized in that: described oxidation inhibitor is four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester.
4. thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material according to claim 1, is characterized in that: the maleic anhydride grafts that described interfacial compatibilizer is ethene-hexene copolymer, or be the maleic anhydride grafts of ethylene-octene copolymer.
5. a method of preparing the thermoplasticity oil resistant halogen-free low-smoke flame-resistant polyolefin cable material of claim 1-4 any one, it is characterized in that: by described matrix resin, fire retardant, lubricant and oxidation inhibitor after high-speed mixer fully mixes, on parallel dual-screw extruding machine, at 125～145 ℃, processing temperature interval, mix and extrude, earnestly granulation.
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| TWI627212B (en) * | 2015-12-14 | 2018-06-21 | 藤倉股份有限公司 | Flame retardant resin composition and metal cable, optical fiber cable and molded article using the same |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397380A (en) * | 2008-09-09 | 2009-04-01 | 苏州德尔泰高聚物有限公司 | High temperature resistant soft low-smoke no-halogen flame-proof polyolefine cable material |
-
2012
- 2012-06-20 CN CN201210204186.3A patent/CN102731891B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397380A (en) * | 2008-09-09 | 2009-04-01 | 苏州德尔泰高聚物有限公司 | High temperature resistant soft low-smoke no-halogen flame-proof polyolefine cable material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI627212B (en) * | 2015-12-14 | 2018-06-21 | 藤倉股份有限公司 | Flame retardant resin composition and metal cable, optical fiber cable and molded article using the same |
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